The use of organopolysiloxanes for the preparation of hair tonics and other hair care preparations is well known. In "Chemie und Technologie der Silicone" (Chemistry and Technology of the Silicones), by Walter Noll, Verlag Chemie, 2nd edition, 1968, page 536, however, it is stated that the objective of maintaining the hairdo independent of the effects of moisture cannot be accomplished with normal polydimethylsiloxanols. Rather, the silicone must be fixed on the hair with the help of functional groups.
German Auslegeschrift No. 1,493,384, discloses organosiloxane compounds or compound mixtures of the formula ##STR4## in which R represents hydrogen or CH.sub.3, X is halogen and x=1 to 10 and y=0 to 8.5, y:x not being larger than 8.5:1.
These organosiloxanes with quaternary ammonium groups can be synthesized by reacting epoxysiloxanes of the formula ##STR5## in a known manner with dimethylamine and converting the resulting dimethylaminoorganosiloxane of formula ##STR6## in a known manner with a hydrogen halide or with a methyl halide into the quaternary ammonium compound of the aforementioned formula.
According to U.S. Pat. No. 4,185,087, the aforementioned organopolysiloxanes with quaternary ammonium groups can be used for hair care preparations. It is stated in the patent that while simple, aqueous shampoos can release dirt and remove an excess of fat from the hair, most shampoos however remove fat so thoroughly from the hair that damage to the hair can be observed. The patent asserts that after being washed, the hair becomes electrostatically charged and therefore difficult to comb.
The patent also teaches that the addition of lanolin derivatives, glycol, fatty acid esters or proteins improves the manageability of the hair after washing. At the same time, however, the additions interfere with foaming during washing. The hair, pursuant to the patent, becomes somewhat sticky and does not feel natural.
The additions do not improve the ability to comb the washed hair, the stability of the hairdo and the gloss of the hair.
The starting materials for the preparation of the compounds described in the German Auslegeschrift No. 1,493,384 are the corresponding methylhydrogenpolysiloxanes. These generally are equilibrated mixtures, that is, siloxane mixtures, in which the number of methylhydrogensiloxy and dimethylsiloxy units corresponds to a random (statistical) distribution. Therefore, in siloxanes in which x has a low value, the proportion of such siloxanes in which x=0 cannot be disregarded. This means in turn that a proportion of unmodified silicone oils is unavoidably present in products of this method. This proportion, however, does not contribute to improving the ability to comb the hair or to improving the hairdo or the gloss of the hair.
It is a further disadvantage of the compounds described in the German Auslegeschrift No. 1,493,384 that the dimethylsiloxy chains are always interrupted by methylsiloxy groups which have lateral quaternary nitrogen groups. The typical siloxane character which is desirable for improving the properties of the hair, is, however, based particularly on the presence of dimethylsiloxy chains. The optimum ability to comb the hair and the optimum gloss are therefore not assured.
Similar teachings arise out of the European Pat. No. 0,017,121 (corresponding to the German Offenlegungsschrift No. 2,912,485). Here also, organopolysiloxanes with quaternary ammonium groups are described in shampoos and hair care preparations to improve the properties of the hair. The compounds correspond to the general formula ##STR7## in which R.sub.1 and R.sub.2 represent alkyl groups with 1 to 4 carbon atoms or an aryl group, p represents the numbers from 0 to 50 and R the ##STR8## group or the ##STR9## group, in which R.sub.3 is an alkyl or hydroxyalkyl group with 1 to 3 carbon atoms, R.sub.4 is R.sub.3 or aryl--CH.sub.2 -- or the allyl group, R.sub.5 is hydrogen or methyl, X.sup..crclbar. represents the anions Cl.sup..crclbar., Br.sup..crclbar., I.sup..crclbar., CH.sub.3 SO.sub.4.sup..crclbar. or C.sub.2 H.sub.5 SO.sub.4.sup..crclbar., m represents numbers from 2 to 10 and n the numbers from 2 to 4.
It is a disadvantage of these compounds that, for small values of p, to wit with relatively low molecular weights, they can easily be washed out, since the organic character of the compounds predominates and their substantivity is slight. At high molecular weights, the properties of the dimethylsiloxy units increasingly predominate, while the influence of the quaternary ammonium groups decreases. In view of the desired application properties, it is therefore necessary to adhere to a relatively narrow molecular weight range if the balance of desired properties is to be assured.
German Offenlegungsschrift No. 3,340,708 discloses polyquaternary polysiloxane polymers which essentially consist of the following, recurring units of the general formula ##STR10## wherein A is an .alpha.,.omega.-bis-alkoxypolysiloxane group or a linear or branched, saturated or unsaturated hydrocarbon chain which contains up to 6 consecutive carbon atoms and which has one or several hydroxy group(s) and may be interrupted by one or several oxygen atom(s) and/or by one or several aromatic ring(s);
R.sub.1, R.sub.2, R.sub.3 and R.sub.4 may be the same or different and represent a C.sub.1-6 alkyl group or a phenyl group; PA0 R.sub.5 is a methyl, ethyl or hydroxyethyl group; PA0 R.sub.6 is a C.sub.1-18 alkyl group or a bivalent --CH.sub.2 -- group. In the latter case the two R.sub.6 groups are joined to each other and, together with the two nitrogen atoms and the A group, which represents a --CH.sub.2 --CH.sub.2 -- group, form a bivalent piperazino group; PA0 or the R.sub.5 and R.sub.6 groups, each represent a --CH.sub.2 group and, together with the two nitrogen atoms and the A group, which represents a CH.sub.2 --CH.sub.2 group, form a bivalent triethylenediamino group; PA0 or the R.sub.5 and R.sub.6 are joined together and, together with the nitrogen atom to which they are linked, form a heterocyclic compound, such as, for example, a compound with a piperidine, morpholine or pyrrolidine ring; PA0 Y.sup.- represents a Cl.sup.- --, Br.sup.- --, CH.sub.3 SO.sub.3.sup.- -- or ##STR11## anion m is a whole number from 1 to 6 and PA0 p is a whole number or a decimal number from 1 to 50. PA0 (A) a siloxane of the general formula EQU R.sub.a X.sub.3-a Si(OSiX.sub.2).sub.n (OSiX.sub.b R.sub.2b).sub.m OSiX.sub.3-a R.sub.a PA0 in which R is described only by its purpose as a functional group which brings about adhesion to the hair, such as an amino, carboxylic acid or quaternary ammonium group. X is hydrogen or a phenyl, hydroxyl or saturated hydrocarbon group with 1 to 8 carbon atoms, a has a value of 0 to 3, b has a value of 0 to 1 and n+m has a value of 1 to 1999, n having a value of from 0 to 2000 and m having a value of from 1 to 2000, PA0 (B) a surfactant PA0 (C) an addition to improve the freeze/thaw stability and PA0 (D) water. PA0 Y is a bivalent hydrocarbon group with at least 2 carbon atoms which has a hydroxyl group and which may be interrupted by an oxygen or nitrogen atom, PA0 R.sup.1, R.sup.2, R.sup.3, R.sup.4 are the same or different and are alkyl groups with at least 1 to 4 carbon atoms or benzyl groups or in which R.sup.1 and R.sup.3 or R.sup.2 and R.sup.4 may be components of a bridging alkylene group, PA0 A is an inorganic or organic anion, PA0 n=5 to 200 PA0 m is a whole number .gtoreq.1. PA0 Z.sup.1 may also represent the following group: ##STR16## Finally, Z.sup.1 may also represent the group ##STR17## wherein R.sup.5 is an alkyl group with 1 to 20 carbon atoms.
Polyquaternary polysiloxane polymers of this type do not have the above described disadvantages of compounds of the German Offenlegungsschrift No. 2,912,485. The practical use of these compounds is, however, opposed by their complicated manufacturing method which requires considerable expenditure. The compounds can be synthesized in yields of .ltoreq.60% of the theoretical, which cannot be justified economically.
Finally, reference is made to the published European patent application No. 0,095,238, which is directed to a composition having essentially the following components: